| 1. |
- Lutz, Anna, 1986, et al.
(author)
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Gas to Particle Partitioning of Organic Acids in the Boreal Atmosphere
- 2019
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In: Acs Earth and Space Chemistry. - : American Chemical Society (ACS). - 2472-3452. ; 3:7, s. 1279-1287
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Journal article (peer-reviewed)abstract
- Gas to particle partitioning of carboxylic acids was investigated using a high-resolution chemical ionization time-of-flight mass spectrometer (HR-CI-ToF-MS) with the filter inlet for gases and aerosol (FIGAERO). Specifically, the partitioning coefficients of 640 components with unique molecular composition were calculated from an assumed linear relationship between [particle]/[gas] versus the mass of the organic fraction (M-org) according to Raoult's law, i.e., equilibrium phase partitioning. We demonstrate that, using the full data set, most of the compounds do not follow a linear relationship. This is especially the case for low- and high-molecular-weight species. Using a subset of the data, with concurrent low sulfate ambient observations ([SO42- < 0.4 mu g m(-3)), the relationship improved significantly and K-i could be derived from the slope of a linear regression to the data. The 100 species with the highest R-2 (>= 0.7) of this regression are presented. The restrictions during high sulfate conditions can be explained by changes in either the equilibrium conditions (e.g., the activity coeffient, gamma(i)) or uptake kinetics (mass transfer limitation). This study demonstrates that partitioning of compounds in the complex ambient atmosphere follows ideal Raoult's law for some limited conditions and stresses the need for studies also in more polluted environments.
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| 2. |
- McFiggans, Gordon, et al.
(author)
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Secondary organic aerosol reduced by mixture of atmospheric vapours
- 2019
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In: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 565:7741, s. 587-593
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Journal article (peer-reviewed)abstract
- Secondary organic aerosol contributes to the atmospheric particle burden with implications for air quality and climate. Biogenic volatile organic compounds such as terpenoids emitted from plants are important secondary organic aerosol precursors with isoprene dominating the emissions of biogenic volatile organic compounds globally. However, the particle mass from isoprene oxidation is generally modest compared to that of other terpenoids. Here we show that isoprene, carbon monoxide and methane can each suppress the instantaneous mass and the overall mass yield derived from monoterpenes in mixtures of atmospheric vapours. We find that isoprene 'scavenges' hydroxyl radicals, preventing their reaction with monoterpenes, and the resulting isoprene peroxy radicals scavenge highly oxygenated monoterpene products. These effects reduce the yield of low-volatility products that would otherwise form secondary organic aerosol. Global model calculations indicate that oxidant and product scavenging can operate effectively in the real atmosphere. Thus highly reactive compounds (such as isoprene) that produce a modest amount of aerosol are not necessarily net producers of secondary organic particle mass and their oxidation in mixtures of atmospheric vapours can suppress both particle number and mass of secondary organic aerosol. We suggest that formation mechanisms of secondary organic aerosol in the atmosphere need to be considered more realistically, accounting for mechanistic interactions between the products of oxidizing precursor molecules (as is recognized to be necessary when modelling ozone production).
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| 3. |
- Bannan, T. J., et al.
(author)
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A method for extracting calibrated volatility information from the FIGAERO-HR-ToF-CIMS and its experimental application
- 2019
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In: Atmospheric Measurement Techniques. - : Copernicus GmbH. - 1867-1381 .- 1867-8548. ; 12:3, s. 1429-1439
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Journal article (peer-reviewed)abstract
- The Filter Inlet for Gases and AEROsols (FIGAERO) is an inlet specifically designed to be coupled with the Aerodyne High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS). The FIGAERO-HR-ToF-CIMS provides simultaneous molecular information relating to both the gas- and particle-phase samples and has been used to extract vapour pressures (VPs) of the compounds desorbing from the filter whilst giving quantitative concentrations in the particle phase. However, such extraction of vapour pressures of the measured particle-phase components requires use of appropriate, well-defined, reference compounds. Vapour pressures for the homologous series of polyethylene glycols (PEG) ((H-(O-CH 2 CH 2 ) n -OH) for n = 3 to n = 8), covering a range of vapour pressures (VP) (10 -1 to 10 -7 Pa) that are atmospherically relevant, have been shown to be reproduced well by a range of different techniques, including Knudsen Effusion Mass Spectrometry (KEMS). This is the first homologous series of compounds for which a number of vapour pressure measurement techniques have been found to be in agreement, indicating the utility as a calibration standard, providing an ideal set of benchmark compounds for accurate characterization of the FIGAERO for extracting vapour pressure of measured compounds in chambers and the real atmosphere. To demonstrate this, single-component and mixture vapour pressure measurements are made using two FIGAERO-HR-ToF-CIMS instruments based on a new calibration determined from the PEG series. VP values extracted from both instruments agree well with those measured by KEMS and reported values from literature, validating this approach for extracting VP data from the FIGAERO. This method is then applied to chamber measurements, and the vapour pressures of known products are estimated. © 2019 Author(s).
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| 4. |
- Le Breton, Michael, 1986, et al.
(author)
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Application of a FIGAERO ToF CIMS for on-line characterization of real-world fresh and aged particle emissions from buses
- 2019
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In: Aerosol Science and Technology. - : Informa UK Limited. - 0278-6826 .- 1521-7388. ; 53:3, s. 244-259
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Journal article (peer-reviewed)abstract
- © 2019, © 2019 The Author(s). Published with license by Taylor & Francis Group, LLC. On-line chemical characterization of real-world particle emissions from 13 transit buses was performed using a chemical ionization mass spectrometer (CIMS) equipped with a filter inlet for gases and aerosols (FIGAERO). In addition to the fresh emissions the emissions were artificially aged using a potential aerosol mass reactor (Go:PAM). The buses studied were running on different fuel types (diesel, compressed natural gas, and rapeseed methyl ester) and exhaust after-treatment systems (selective catalytic reduction (SCR), exhaust gas recirculation (EGR), and a three-way catalyst). When evaluating emissions from passing exhaust plumes using the FIGAERO ToF-CIMS, two technical features were highlighted from this work, the use of high mass calibrants and the factor enhancement method to be able to filter important compounds from mass spectra including hundreds of species. Here, acetate was used as the reagent ion to enable detection of highly oxygenated species in the exhaust particle emissions with potential high toxicity and/or secondary organic aerosol formation (SOA) potential. The acetate ionization scheme accounted for 4% to 46% of the total emitted particulate mass through identification of 61 species in the spectra. For aged emission the various fuel types provided overlapping species that could explain up to 19% of the aged emissions. This is hypothesized to come from the oxidation of engine lubrication oil, thus a common source for various fuels which was further supported by laboratory measurements. Specific markers from the SCR technology, such as urea oxidation products and further byproducts from hydrolysis were identified and attributed to reactions of isocyanic acid.
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| 5. |
- Salvador, Christian Mark, 1989, et al.
(author)
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Ambient nitro-aromatic compounds - biomass burning versus secondary formation in rural China
- 2021
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In: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 21:3, s. 1389-1406
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Journal article (peer-reviewed)abstract
- Nitro-aromatic compounds (NACs) were measured hourly at a rural site in China during wintertime to monitor the changes due to local and regional impacts of biomass burning (BB). Concurrent and continuous measurements of the concentrations of 16 NACs in the gas and particle phases were performed with a time-of-flight chemical ionization mass spectrometer (CIMS) equipped with a Filter Inlet for Gases and AEROsols (FIGAERO) unit using iodide as the reagent ion. NACs accounted for <2 % of the mass concentration of organic matter (OM) and total particulate matter (PM), but the total particle mass concentrations of these compounds can reach as high as 1000 ng m(-3) (299 ng m(-3) avg), suggesting that they may contribute significantly to the radiative forcing effects of atmospheric particles. Levels of gas-phase NACs were highest during the daytime (15:00-16:00 local time, LT), with a smaller night-time peak around 20:00LT. Box-model simulations showed that this occurred because the rate of NAC production from gas-phase sources exceeded the rate of loss, which occurred mainly via the OH reaction and to a lesser degree via photolysis. Data gathered during extended periods with high contributions from primary BB sources (resulting in 40 %-60 % increases in NAC concentrations) were used to characterize individual NACs with respect to gas-particle partitioning and the contributions of regional secondary processes (i.e. photochemical smog). On days without extensive BB, secondary formation was the dominant source of NACs, and NAC levels correlated strongly with the ambient ozone concentration. Analyses of individual NACs in the regionally aged plumes sampled on these days allowed precursors such as phenol and catechol to be linked to their NAC derivatives (i.e. nitrophenol and nitrocatechol). Correlation analysis using the high time resolution data and box-model simulation results constrained the relationships between these compounds and demonstrated the contribution of secondary formation processes. Furthermore, 13 of 16 NACS were classified according to primary or secondary formation process. Primary emission was the dominant source (accounting for 60 %-70 % of the measured concentrations) of 5 of the 16 studied NACs, but secondary formation was also a significant source. Photochemical smog thus has important effects on brown carbon levels even during wintertime periods dominated by primary air pollution in rural China.
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| 6. |
- Anderson, D. C., et al.
(author)
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Formaldehyde in the Tropical Western Pacific: Chemical Sources and Sinks, Convective Transport, and Representation in CAM-Chem and the CCMI Models
- 2017
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In: Journal of Geophysical Research-Atmospheres. - : American Geophysical Union (AGU). - 2169-897X. ; 122:20, s. 11201-11226
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Journal article (peer-reviewed)abstract
- Formaldehyde (HCHO) directly affects the atmospheric oxidative capacity through its effects on HOx. In remote marine environments, such as the tropical western Pacific (TWP), it is particularly important to understand the processes controlling the abundance of HCHO because model output from these regions is used to correct satellite retrievals of HCHO. Here we have used observations from the Convective Transport of Active Species in the Tropics (CONTRAST) field campaign, conducted during January and February 2014, to evaluate our understanding of the processes controlling the distribution of HCHO in the TWP as well as its representation in chemical transport/climate models. Observed HCHO mixing ratios varied from similar to 500 parts per trillion by volume (pptv) near the surface to similar to 75 pptv in the upper troposphere. Recent convective transport of near surface HCHO and its precursors, acetaldehyde and possibly methyl hydroperoxide, increased upper tropospheric HCHO mixing ratios by similar to 33% (22 pptv); this air contained roughly 60% less NO than more aged air. Output from the CAM-Chem chemistry transport model (2014 meteorology) as well as nine chemistry climate models from the Chemistry-Climate Model Initiative (free-running meteorology) are found to uniformly underestimate HCHO columns derived from in situ observations by between 4 and 50%. This underestimate of HCHO likely results from a near factor of two underestimate of NO in most models, which strongly suggests errors in NOx emissions inventories and/or in the model chemical mechanisms. Likewise, the lack of oceanic acetaldehyde emissions and potential errors in the model acetaldehyde chemistry lead to additional underestimates in modeled HCHO of up to 75 pptv (similar to 15%) in the lower troposphere.
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| 7. |
- Bannan, T. J., et al.
(author)
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A Large Source of Atomic Chlorine From ClNO2 Photolysis at a UK Landfill Site
- 2019
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In: Geophysical Research Letters. - : American Geophysical Union (AGU). - 0094-8276 .- 1944-8007. ; 46:14, s. 8508-8516
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Journal article (peer-reviewed)abstract
- Nitryl chloride (ClNO2) acts as a source of highly reactive chlorine atoms as well as an important NOx reservoir. Measurements of ClNO2 at an operational U.K. landfill site are reported here for the first time. A peak concentration of 4 ppb of ClNO2 was found with a peak mean nighttime maximum of 0.9 ppb. Using models based upon the photolysis of observed ClNO2 and atmospheric chlorine chemistry, chlorine atom concentrations reaching in excess of 1.20 x 10(5) molecules/cm(3) in the early morning following sunrise are calculated. These concentrations are approximately 10 times higher than previously reported in the United Kingdom, suggesting a significant impact on the oxidizing capacity around such sites. Given the ubiquity of landfill sites regionally and globally, and the large abundances of Cl atoms from the photolysis of ClNO2, chlorine chemistry has a significant impact on ozone formation and volatile organic compounds oxidation as shown by WRF-Chem modeling. Plain Language Summary Landfill sites are a known source of traces gases into the atmosphere, but measurements often focus predominately on methane and carbon dioxide. A small subsection of trace gas measurements at landfill sites have shown, however, that these sites may be important halogen sources that could have subsequent impacts on air quality and climate. Spatially limited field measurements have previously been reported of a halogen species, ClNO2, showing that this species is consistently formed during nighttime hours, but no such measurements before now have been made at any landfill site. ClNO2 undergoes photolysis upon sunrise, releasing the extremely reactive Cl as well as NO2 into the atmosphere and therefore plays an important part in the total budget and distribution of tropospheric oxidants, halogens, and reactive nitrogen species, all of which are important to air quality. Here we present mass spectrometry measurements of ClNO2 taken at an undisclosed landfill, which show high concentrations in comparison to any other global study of this type. We use predictive modeling techniques to show the importance of this halogen species to air quality, using indicators such as ozone formation. Based on these results we recommend that landfill sources of Cl should be included in future air quality studies.
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| 8. |
- Faxon, Cameron, et al.
(author)
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Characterization of organic nitrate constituents of secondary organic aerosol (SOA) from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry
- 2018
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In: Atmospheric Chemistry And Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 18, s. 5467-5481
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Journal article (peer-reviewed)abstract
- The gas-phase nitrate radical (NO 3 • ) initiated oxidation of limonene can produce organic nitrate species with varying physical properties. Low-volatility products can contribute to secondary organic aerosol (SOA) formation and organic nitrates may serve as a NO x reservoir, which could be especially important in regions with high biogenic emissions. This work presents the measurement results from flow reactor studies on the reaction of NO 3 • with limonene using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS) combined with a Filter Inlet for Gases and AEROsols (FIGAERO). Major condensed-phase species were compared to those in the Master Chemical Mechanism (MCM) limonene mechanism, and many non-listed species were identified. The volatility properties of the most prevalent organic nitrates in the produced SOA were determined. Analysis of multiple experiments resulted in the identification of several dominant species (including C 10 H 15 NO 6 , C 10 H 17 NO 6 , C 8 H 11 NO 6 , C 10 H 17 NO 7 , and C 9 H 13 NO 7 ) that occurred in the SOA under all conditions considered. Additionally, the formation of dimers was consistently observed and these species resided almost completely in the particle phase. The identities of these species are discussed, and formation mechanisms are proposed. Cluster analysis of the desorption temperatures corresponding to the analyzed particle-phase species yielded at least five distinct groupings based on a combination of molecular weight and desorption profile. Overall, the results indicate that the oxidation of limonene by NO 3 • produces a complex mixture of highly oxygenated monomer and dimer products that contribute to SOA formation.
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| 9. |
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| 10. |
- Le Breton, Michael, 1986, et al.
(author)
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Chlorine oxidation of VOCs at a semi-rural site in Beijing: significant chlorine liberation from ClNO2 and subsequent gas- and particle-phase Cl-VOC production
- 2018
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In: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 18:17, s. 13013-13030:18, s. 13013-13030
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Journal article (peer-reviewed)abstract
- Nitryl chloride (ClNO2) accumulation at night acts as a significant reservoir for active chlorine and impacts the following day's photochemistry when the chlorine atom is liberated at sunrise. Here, we report simultaneous measurements of N2O5 and a suite of inorganic halogens including ClNO2 and reactions of chloride with volatile organic compounds (Cl-VOCs) in the gas and particle phases utilising the Filter Inlet for Gas and AEROsols time-of-flight chemical ionisation mass spectrometer (FIGAERO-ToF-CIMS) during an intensive measurement campaign 40 km northwest of Beijing in May and June 2016. A maximum mixing ratio of 2900 ppt of ClNO2 was observed with a mean campaign nighttime mixing ratio of 487 ppt, appearing to have an anthropogenic source supported by correlation with SO2, CO and benzene, which often persisted at high levels after sunrise until midday. This was attributed to such high mixing ratios persisting after numerous e-folding times of the photolytic lifetime enabling the chlorine atom production to reach 2.3 x 10(5) molecules cm(-3) from ClNO2 alone, peaking at 09:30 LT and up to 8.4 x 10(5) molecules cm(-3) when including the supporting inorganic halogen measurements. Cl-VOCs were observed in the particle and gas phases for the first time at high time resolution and illustrate how the iodide ToF-CIMS can detect unique markers of chlorine atom chemistry in ambient air from both biogenic and anthropogenic sources. Their presence and abundance can be explained via time series of their measured and steady-state calculated precursors, enabling the assessment of competing OH and chlorine atom oxidation via measurements of products from both of these mechanisms and their relative contribution to secondary organic aerosol (SOA) formation.
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